CA1295312C - Method of producing a spherical support for alphaolefin polymerisation catalyst - Google Patents

Abstract

The invention relates to the manufacture of a spherical catalyst support for the polymerization of alphaolefins, by reacting a mixture of a chlorinated organic compound and an electron donor, with a mixture of an alkylmagnesium with an aluminoxane. and / or aluminosiloxane, optionally in the presence of an electron donor identical or different to that associated with the chlorinated organic compound. The support obtained is subjected to a second activation with a chlorinated compound before being impregnated with a transition metal halide to obtain the desired catalyst.

Description

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The present invention relates to a method of manufacture of a spherical catalyst support polymerization of alpha-olefins by reaction of a mixture a chlorinated organic compound and an electron donor on a mixture of an alkylmagnesium and an aluminoxane and / or aluminosiloxane, followed by an effective activation treatment killed with a chlorine compound. The spherical support as well obtained by the process according to the invention can be "converted"
as a catalyst for the polymerization of alpha-olefins by simple impregnation of a titanium halide. The catalyst thus obtained then makes it easy to manufacture polyolefins with a broad molecular distribution in the presence of cocatalyst in the polymerization or copolymerization of alpha-olefins of formula CH2 = CHR in which R is a hydrogen atom or an alkyl radical containing from 1 to 6 carbon atoms.
In the French public patent no. 2,529,207 are described spherical supports for the manufacture of alpha-olefin polymerization catalysts. These supports are obtained by reaction with an organic compound chlorinated, necessarily in the presence of an ether oxide and a organomagnesium Rl Mg R2, x Al (R3) 3 1 2 3 alkyl radicals.
This method of preparing the support allows obtaining a catalyst, the polymers of which are produced in its presence have a molecular weight distribution narrow or slightly dispersed.
The present invention provides a new process for the production of a spherical catalyst support for the preparation of a spherical catalyst polymerization of alpha-olefins, consisting, in a first stage, first mix a kylmagnesian a with a aluminoxane, an aluminosiloxane or a mixture of the two, the Mg / Al molar ratio being between 5 and 200, then to do ~ 3 ~

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- lo-react.i: r said mixture with a mixture of an organic compound chlorinated and an electron donor, sufficient for the chlorine concelltration be such as the molar ratio Cl / Mg is at least 2, ledi-t electron donor included 5 at least one aliphatic or cyclic ether, and being present in quant: ity such that the molar ratio of the quantity total magnesium electron donor is between 0, Ql and 5, it being understood that the molar ratio of ether aliphatic or cycli ~ lle on magnesium is minimltm of 0.01, for a second stage, to be resuspended the suppor obtained to make him undergo a new activation with an inorganic or organic chlorine compound;
said alkylmagnesium having the formula RlMgR2 in the ~ uelle Rl and R2 are alkyl radicals having from l to : L5: L2 carbon atoms;
ledi.t aluminoxane having the formula:

R '\ / ~' / ~ lV- [Al-O] -nAl \

in which R 'is an alkyl radical having from 1 to 16 car ~ one atoms, the R "together forming a radical - O -or each representing a radical R 'and n being a number 25 enkier from 0 to 20; and said aluminosiloxane having the formula:

\ Al-0-Si \ R4 in which Rl, R2, R3, R ~ and R5, identiclues or di ~ ferents, represent an alkyl radical having from 1 to 12 carbon atoms, hydrogen or chlorine, knowing ~ E ~

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that there are no more than three hydrogen atoms or chlorine per mole of aluminosiloxane ~
Due to the presence of the aluminoxane and / or : aluminosiloxane in the first stage of the process according to the invention the support obtained by the process according to the invention `then later imbued with elements catalytic active, already alone influences the molecular distribution of the polymer finally obtained in presence of this catalyst.
10 Activation of the support by a chlorinated compound in the second stage of the process according to the invention makes it possible to . complete the quality of the catalyst thus obtained in the ;.; measure as it ensures the morphology of the support remains intact and the ----. ...

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2 ~ 2 productivity is improved. This also makes it possible to increase the mass apparent volume of the final polymer.
In more detail the alkylmagnesian is previously mixture with aluminoxane and / or aluminosiloxane, preferably solution in an inert solvent such as a hydrocarbon such as hexane, possibly in the presence of an e donor: Lectrons. Once completed the mixture, we react the organic compound chlorine diluted in a electron donor. At the end of the reaction, the spherical support ,; lO form, suspended in the reaction medium ~ el, is filtered, washed with a light liquid, then finally dry. We thus obtain a support spherical having a specific surface c ~ mprlse between 1 and 100 m / g and whose average particle diameter is between 5 ~ and 100 microns and plU8 generally between 10 and 50. The width of , ~ IS particle size distribution of the supports, and consequently subsequent catalysts is very narrow, generally less than 5.
This particle size distribution width is characterized by the diameter ratio 95% to 5%: diameters taken on the curve `granulo ~ etric distribution given in cumulative percentage as a function ~,:
increasing particle diameters.
~ `The mls alkylmagnesian used corresponds to the formula Rl Mg R2 in which Rl and R2 are alkyl radicals having from I to 12 , carbon atoms.
The aluminoxane which can enter into the composition of the support is chosen from products corresponding to the formula:

\ A1 ~ 0 - ~ 1 - 0 ~ Al in which R 'is an alkyl radlcal having from I to 16 atoms of carbon, the R "together forming a radical -0- or representing each a radical R ', and, n being an integer from 0 to 20.
The aluminosiloxane can enter into the composition of support is chosen from products corresponding to the formula:

\ Al -0- Si / R
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; 3 `in which R1, R2, R3, R4, R5, identical or different, represent try an alkyl radical having from 1 to 12 atoms, and mleux, from 1 to 6 carbon atoms, or even sachan hydrogen ~ that preferably there there are no more than three hydrogen atoms per mole of derivative, or finally chlorine knowing that preferably there are no more trols moles of chlorine per mole of derivative.
The chlorinated organic compound, se ~ an ~ of chlorinating agent ;; ~ déri ~ e of the alkylmagnesian of the aluminum compound, is chosen from alkyl chlorides in which the alkyl radical is primary, secondary or tertiary, among alkyl polyhalides or by ~ i chlor ~ acid res.
The preferred compounds are ~ ertiobutyl chloride, n-butyl chloride, dichlorethane, thionyl chloride, l Benzoyl chloride.
`The chlorinating agent of the mixture of alkylmagnesien and - organic compound of aluminum is associated with at least one donor ,. , ~
of cholsi electrons among aliphatic or cyclic ethers among which may be cited diisoamyl ether, dry sec-butyl.
The electron donor possibly as60cié a ~ mixture of alkylmagrLesien and the organic compound of alumlnium is pre-identical to the donor of electro ~ s associated with the chlorinating agene.
However, it is not excluded to associate any compound with this mixture.
known as an electron donor. It is advantageously chosen from aliphatic or aromatic carboxylic acids and their esters alkyl, aliphatic or cyclic ethers, ketones, vinyl esters, acrylic derivatives, in particular acrylates or alkyl methacrylates, and silanes. Notably noted as electron donors, such as methyl paratoluate, ethyl benzoate, ethyl or butyl acetate, ethyl ether, ethyl para-anisate, dibutylphthalate, dioctyphthalate, diisobuty-phthalate, tetrahydrofuran, dioxane, acetone, methyl isobutyl ketone.
vinyLe acetate, methyl methacrylate, and phenyltrlethoxysilane.
Esters can also be used as products addition with halides of Lewis acids different from magnesium dihalides.
In order to properly control the morphology of the flnal port). 11 it is important to associate the components to each other in quantlte : ~ "
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appropriate.
This is how the recommended Mg / Al molar ratio is between: 5 and 200 and mleux between 10 and 80. Likewise a concentration sufficient tratlon of organic chlorine compound during the first chloratlon does not allow to reach a sufficient chlorination degree of the organomagueslen derivative which leads to a support containing a too much organic compounds. The concentration in chlorine to be used in this step is preferably such that the Cl / Mg molar ratio is between 2 and 4.
The amount of electron donor to be used can ; be such that the molar ratio of the totality of the donor trons on the r ~ aguesium is between 0.01 and 5 knowing that the ratio of aliphatic or cyclic ether ~ ur magnesium is at minimum 0.01.
The supports obtained according to the invention are particularly suitable for the manufacture of catalysts ~, Ziegler-Natta, of polymerl ~
sation of alpha-olefins based on transition metal halide such as Cr, V, Zr and better Ti. These catalysts result ~
general impregnatio ~ of an MgC12 support by, for example, TiC14.
Cornme from ~ to signaled, before impregnating the support by the transition metal halide, it is recommended to subject it to a new activation by a second treatment ~ by a chlorine compound. To do this, the support is resuspended, eventuelleme ~ t in an inert liquid such as a hydrocarbon sl the chlorine compound is insufficiently fluid, and then brought back to contact with a chlorinated compound so as to ensure total chlorination of the support and in particular metal-carbon bonds. The quality of this chlorination can be followed by the hydrolysis of the resulting support so much. In the case of an overchlorination of the support, the quantity of halogen to implement does not matter, any excess may later be remove by possible washing.
The colored compound used in this step is identified than or different from the one previously used. In this case it can ~ 5 being not only an organic compound but also an inorganic compound halogenated picnic. It can be for example: ~ ICl, a hydrocarbon halogen such CCI4, or SiC14, S ~ C12.

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35i3 ~ 2 This stage completed, the support, after possibly : ~ filtration, washing and light drying, is `impregnated with halide transitlon metal plus partlcuLièremerlt of formula Ti (OR) X4 where R
is an alkyl radical of 1 to 12 carbon atoms and X is a halogen, and, preferably TiCl4. The impregnation can be done classi ~ ue by adding to the support a sufficient quantity of halide of transition metal optionally in a lnte solvent to fo ~ ter a homogeneous suspension ~ e. In general, the Maltian suspended under stirring for about a few hours at a lower temperature at 150C is sufficient to impregnate the transition metal halide support tion. The catalyst is then filtered and washed with inert inert liquid.
until elimination in the liquid of any trace of halide. he is not excluded at this ~ tade to perform a second impregnation halide of ~ traumatic tetal ~, followed by ure fll ~ ration and washing, to modify the kinetics of the catalyst and the properties physicochemicals of polymers resulted ~ t.
Co ~ editions of polymerization of alpha-olefLnes n ~ ec Les catalysts according to the invention ~ ion are those of ~ to co ~ naked in the art prior. The polymerization can be carried out either in liquid phase whether or not an inert solvent hydrocarbon, such as hexane or heptane, or elt gas phase. The temperature of the polymerization is generally between 40 and 150C and in particular between 50 and 90C. The polymerization can also be carried out en masse under pressures from 100 to 1300 bar between 130 and 350C.
The polymers obtained with these catalysts are present under spherical particles which gives them a characteristic high flow ristics.
The tests of the following example illustrate the invention without however limit it.

A. PREPARATION OF THE SUBSTRATE
We operate in a glass reactor of 1 liter purge at the teote, equipped with a stirring and regulation device temperature. In this reactor, under constant scanning of a ~ ote ~ have introduced an alkylmagnesium compound, aluminoxane or aLuminosi-loxane, a first electron donor, scche hexane in quantity sufficient to complete the volume of the circ ie a concentration :
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`6 tration in Mg of 0.5 mole per liter. This solution is kept under ; stirring at 50C for approximately 16 hours.
A mixture of electron donor and tertiary chloride butyl is ln ~ ecte slowly by means of a syringe mounted on infuser. In ~ ection ends the agitatlon and the temperature is maintained for 3 hours.
; The reaction medium is ~ filtered at room temperature.
After a few washes with hexane the recovered powder can be iO é ~ completely dried under a stream of ~ ote at 60 ~ C (Table A).
B. PREPARATION OF THE CATALYST
The operation is carried out in a 500 ml Yerre reactor. team of a agitation and temperature regulation device. In this purged reactor and under constant nitrogen sweep are introduced the support then either hexane ~ dried and degassed with nitrogen, so as to ; for ~ er a slow stirred porridge ~ t which is bubbled HCl a ~ hydra for 30 minutes at room temperature, solt an agent liquid chlorinator in which the support remains in suspension for one hour at 50C.
20The treated suppo ~ c is filtered, the ~ e with dry hexane and degaze ~ slightly dry. It is then rem ~ s suspenslon homogè ~ e in TiCl4 under agitation which, while remaining weak, must be effective ~ this. The impregnation is carried out at a temperature of 60 - 90C for 2 : hours. The ~ reaction site is then hot filtered; the cataly-retained seur is washed at room temperature with hexane ~ until elimination of all traces of TiC14 in the washing liquid. The catalyst can be dried at around 60C and then stored in an atmosphere inert or maintained in suspension in an inert hydrocarbon (table B).
30C. POLYMERIZATION OF ET ~ YLENE
We operate in a 5 liter stainless steel reactor fitted with a agitator rotating at 500 rpm, and a means of regulating temperature.
In the reactor purged with aYoce are the products under scanning of hydrogen and at room temperature 1000 ml. of hexane and the cocatalyst.
Puls is injected successively into the reactor 4.6 bars of hydrogen, 6.4 bars of ethyl puls 20 to 30 mg of catalytic converter . ''' ~
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suspension in hexane. The temperature of the medium has risen to 80C, , the pressure being kept constant by continuous supply of ethylene.
~ nearly I hour 30 of reaction the polymerization is stopped by S addition of methanol and ~ Cl. The polymer is recovered and dried (table C).
The following tables illustrate these different stages.

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: `ll ~,. =. _ In a reactor of 8.2 1. dry and degassed with nitrogen is introduced under nitrogen and at 350 rpm agltation successively at 40C:
3 1. dry hexane 10.5 n ~ of triisobutylalumlnium (TIBA) diluted in hexane to 2.1 M / l 0.93 g of catalyst 4 of Example 1 - 0.5 bar absolute hydrogen 3 absolute bars of nitrogen After 5 minutes of homogenization, ethylene is introduced to a flow rate of 10 l / h for 30 minutes then 6S l / h for 2 hours.
It arr ~ ete ln ~ roductio ~ ethylene ~ the total pressure drops ~. The reactor is degassed with nitrogen with reduced stirring of 150 revolutions / mln ~ te.
- 15 The temperature is brought to 60C. Hexane is eliminated by nitrogen sweep. After complete evaporation of the solvent, it is collected 164 g of prepoly ~ ere with spherical morphology sa ~ s aggregates, of degree of p ~ epolymerization of 176 g of prepolymer per gram of catalyst and ; apparent density (MVA) of 0.302.
Gas-phase copolymerization of ethylene-butene-1 We operate in a 8.2 l reactor previously dried ~ equipped with a ; agitator rotating at a speed of 400 revolutions / minute and maintained at 85C
throughout the polymerization.
In the reactor maintained under reduced pressure of 1.33 Pa, in presence of 100 g of polyethylene at the bottom of the tank, we inject:
- 1 absolute bar of butene-1 - a mixture with a spheroprotective effect of:
0.4 mM TIBA diluted with 2.1 M / l of hexane and 0.027 mM phenyltriethoxysilane (PTES) - 1.5 bar ahsolu of butene-1 - 2 bars abs ~ read hydrogen - 13.5 bars of ethylene 10 g of the active prepolymer are then introduced into the reactor ; above on which the melan ~ e is impregnated with 0.4 mM of TI ~ A diluted to 2.1 M / l in hexane and 0.027 n ~ of PTES. This introduction to prepoly-mother is carried out by pushing with the a7.0te ~ until the pressure total inside the reactor reaches 21 bar absolute. We maintain the presslon in the re ~ acceur to cece value by Lnjection of echylelle ec . ~
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of butene-1 in a butene-1 / ethylene molar ratio of 0.0466.
After 4 hours of polymerization, the reactor is degassed and cooled.
S We receive ~ lle 928 g of copolymer of spherical morphology, initial charge deducted. The productivity is 16.332 g of polyethylene per g of catalyst.
The characteristics of copoly ~ era are:
MI2 = 0.6 Density = 0.924 050 = 840 microns MVA = Q, 462 g / C ~ 3 ,, ~ a :.

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Claims (8)

1. Method of manufacturing a spherical support of catalyst for the preparation of a spherical catalyst polymerization of alpha-olefins, consisting, in a first stage, first mix an alkylmagnesian with an aluminoxane, an aluminosiloxane or a mixture of two, the Mg / A1 molar ratio being between 5 and 200, then at reacting said mixture with a mixture of a compound chlorinated organic and an electron donor, said compound chlorinated organic being in sufficient quantity for the chlorine concentration is such that the molar ratio C1 / Mg is at least 2, said electron donor including at least one aliphatic or cyclic ether and being present in quantity such that the molar ratio of the quantity total magnesium electron donor be understood between 0.01 and 5, it being understood that the molar ratio aliphatic or cyclic ether on magnesium is at minimum of 0.01, then in a second stage, to put back in suspends the support obtained to subject it to a re-activation with an inorganic chlorine compound or organic;
said alkylmagnesium having the formula R1MgR2 in which R1 and R2 are alkyl radicals having from 1 to 12 carbon atoms;
said aluminoxane having the formula:

in which R 'is an alkyl radical having from 1 to 16 carbon atoms, R "together forming a radical - O -or each representing a radical R 'and n being a number integer from 0 to 20; and said aluminosiloxane having the formula:

in which R1, R2, R3, R4 and R5, identical or different, represent an alkyl radical having from 1 to 12 carbon atoms, hydrogen or chlorine, knowing that there are no more than three hydrogen atoms or chlorine per mole of aluminosiloxane. 2. Method according to claim 1, characterized in that mixing the alkyl magnesium with a aluminoxane, an aluminosiloxane or a mixture of these two compounds is performed in the presence of an electron donor identical or different to that mixed with the organic compound chlorine. 3. Method according to claim 2, characterized in that the electron donors used in the two mixtures are identical. 4. Method according to claim 1, 2 or 3, characterized in that at the end of the first stage of the process, the support obtained is filtered and washed before being put back in suspension in a medium containing the chlorinated compound of so as to subject it to a new activation. 5. Method according to claim 1, 2 or 3, characterized in that at the end of the first stage of the process the support obtained is filtered, washed and dried before being resuspended in a medium containing the compound chlorinated so as to make it undergo a new activation. 6. Method according to claim 1, 2 or 3, characterized in that the amount of organic compound chlorine used in the first stage of the process is chosen so that the chlorine concentration is such that the C1 / Mg molar ratio is between 2 and 4. 7. Method for manufacturing a catalyst polymerization of alpha-olefins, characterized in that impregnates a transition metal halide a support obtained according to the method of claim 1, 2 or 3. 8. Method for manufacturing a catalyst polymerization of alpha-olefins, characterized in that a support obtained according to titanium halide is impregnated the method of claim 1, 2 or 3.